脱氢枞酸缩水甘油酯接枝羟丙基壳聚糖制备及性能研究

doi:10.3969/j.issn.0253-2417.2021.06.007

林产化学与工业 ›› 2021, Vol. 41 ›› Issue (6): 51-56.doi: 10.3969/j.issn.0253-2417.2021.06.007

脱氢枞酸缩水甘油酯接枝羟丙基壳聚糖制备及性能研究

杨欣欣¹^,²(), 郭伟¹^,³, 蔡照胜¹^,*(), 黄旭娟¹, 王婷¹, 丁正青¹

1. 盐城工学院化学化工学院, 江苏盐城 224051
2. 中国林业科学研究院林产化学工业研究所, 江苏南京 210042
3. 江苏大学化学化工学院, 江苏镇江 212000

收稿日期:2020-10-22 出版日期:2021-12-28 发布日期:2021-12-31
通讯作者: 蔡照胜 E-mail:yangxx0316@163.com;jsyc_czs@163.com
作者简介:蔡照胜, 教授, 博士, 硕士生导师, 研究领域为生物质化学改性与利用及精细化学品制备技术开发; E-mail: jsyc_czs@163.com
杨欣欣(1995-), 女, 河南郑州人, 博士生, 研究方向为生物质化学利用; E-mail: yangxx0316@163.com
基金资助:
国家自然科学基金资助项目(32071706);江苏省生物质能源与材料重点实验室开放基金项目(JSBEM201909)

Preparation and Properties of Glycidyl Dehydroabietate Grafted Hydroxypropyl Chitosan

Xinxin YANG¹^,²(), Wei GUO¹^,³, Zhaosheng CAI¹^,*(), Xujuan HUANG¹, Ting WANG¹, Zhengqing DING¹

1. School of Chemistry and Chemical Engineering, Yancheng Institute of Technology, Yancheng 224051, China
2. Institute of Chemical Industry of Forest Products, CAF, Nanjing 210042, China
3. School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212000, China

Received:2020-10-22 Online:2021-12-28 Published:2021-12-31
Contact: Zhaosheng CAI E-mail:yangxx0316@163.com;jsyc_czs@163.com

摘要/Abstract

摘要：

利用甘油磷酸钠（GP）为交联剂，通过羟丙基壳聚糖（HPCS）与脱氢枞酸缩水甘油酯（GDHA）间的接枝反应，制得GDHA接枝HPCS（GDHA-g-HPCS）；用FT-IR、¹H NMR和UV表征中间体和产物结构，元素分析法测定HPCS的取代度（D_S）和GDHA-g-HPCS的接枝度（D_G），表面张力法探讨GDHA-g-HPCS的表面活性，苯-水乳液稳定时间法评价GDHA-g-HPCS的乳化能力，倒瓶法确定GDHA-g-HPCS交联产物的凝胶形成时间。研究结果表明：对于D_S为110.6%的HPCS，当D_G从0.72%增至10.54%时，对应的GDHA-g-HPCS的临界胶束浓度从761.9 mg/L降至189.4 mg/L，但最小表面张力（γ_min）都在45 mN/m左右；GDHA-g-HPCS对苯-水的乳化能力随D_G的增加呈先增后减的趋势；2 g/L的GDHA-g-HPCS（D_G为2.81%）为稳定剂得到的苯-水乳液稳定时间为18 063 s，远大于单硬脂酸甘油脂（单甘脂）、蔗糖脂肪酸酯（蔗糖酯）和脂肪醇聚氧乙烯醚（AEO-9）等为稳定剂时形成的乳液；30 g/L的GDHA-g-HPCS（D_G为2.81%）水溶液用GP交联后，在37 ℃下经26 min即可形成凝胶，且该凝胶具有温敏性，将其置于4.0 ℃的环境中经42 min又重新转化为溶胶。

关键词: 羟丙基壳聚糖, 表面活性, 乳化性能, 温敏凝胶

Abstract:

Glycidyl dehydroabietate grafted hydroxypropyl chitosan (GDHA-g-HPCS) was obtained through the grafting reaction between hydroxypropyl chitosan (HPCS) and glycidyl dehydroabietate (GDHA), and the GDHA-g-HPCS was cross-linked with sodium glycerophosphate as cross-linking agent. The structures of intermediates and products were characterized by FT-IR, ¹H NMR and UV. The degree of substitution (D_S) of HPCS and the grafting degree (D_G) of the GDHA-g-HPCS were determined by elemental analysis. The surface activities of GDHA-g-HPCSs were investigated by surface tension method. The emulsifying abilities of GDHA-g-HPCSs were evaluated according to the stabilization time of emulsion composed of benzene and water with GDHA-g-HPCS as emulsifier. The gel formation time of cross-linked GDHA-g-HPCS was studied by inverted bottle method. When the D_S of HPCS was 110.6% and the D_G increased from 0.72% to 10.54%, the results showed the critical micelle concentration of GDHA-g-HPCSs decreased from 761.9 mg/L to 189.4 mg/L while the minimum surface tension (γ_min) was maintained about 45 mN/m, and the emulsifying ability of GDHA-g-HPCS increased at first and then decreased with the increase of D_G. When the 2 g/L GDHA-g-HPCS with the D_G of 2.81% was utilized as emulsifier, the stabilization time of benzene-water emulsion was 18 063 s much better than that of the emulsion formed by stabilizer, such as monoglyceride, sucrose ester or AEO-9. When the 30 g/L aqueous solution of GDHA-g-HPCS cross-linked by GP, a gel could be formed in 26 minutes at 37 ℃, and could be converted into a sol again in 42 minutes at 4 ℃.

Key words: hydroxypropyl chitosan, surface activity, emulsifying property, temperature-sensitive gel

中图分类号:

TQ35
O629.1

杨欣欣, 郭伟, 蔡照胜, 黄旭娟, 王婷, 丁正青. 脱氢枞酸缩水甘油酯接枝羟丙基壳聚糖制备及性能研究[J]. 林产化学与工业, 2021, 41(6): 51-56.

Xinxin YANG, Wei GUO, Zhaosheng CAI, Xujuan HUANG, Ting WANG, Zhengqing DING. Preparation and Properties of Glycidyl Dehydroabietate Grafted Hydroxypropyl Chitosan[J]. Chemistry and Industry of Forest Products, 2021, 41(6): 51-56.

图/表 6

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表2

参考文献 17

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样品 sample	物料比 material rate	w_C/%	w_N/%	D_S/%	D_G/%
HPCS	0∶1	37.69	4.60	110.60
GDHA-g-HPCSⅠ	1∶1	40.49	4.87	110.60	0.72
GDHA-g-HPCSⅡ	2∶1	42.53	4.86	110.60	2.81
GDHA-g-HPCSⅢ	4∶1	38.21	4.02	110.60	6.64
GDHA-g-HPCSⅣ	6∶1	44.44	4.89	110.60	8.58
GDHA-g-HPCSⅤ	8∶1	44.53	4.34	110.60	10.54

样品sample	C_cmc/(mg·L^-1)	γ_cmc/(mN·m^-1)	γ_min/(mN·m^-1)
GDHA-g-HPCSⅠ	761.9	46.51	45.01
GDHA-g-HPCSⅡ	662.7	46.40	45.03
GDHA-g-HPCSⅢ	413.8	46.44	45.02
GDHA-g-HPCSⅣ	295.5	46.01	45.02
GDHA-g-HPCSⅤ	189.4	45.54	45.01

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脱氢枞酸缩水甘油酯接枝羟丙基壳聚糖制备及性能研究

Preparation and Properties of Glycidyl Dehydroabietate Grafted Hydroxypropyl Chitosan

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